Classifications

• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
  • A01N59/16—Heavy metals; Compounds thereof
  • A01N59/20—Copper
• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
  • A01N37/36—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids

Definitions

• the present invention relates to a germicidal composition for agricultural and horticultural use.
• germicides bactericides/fungicides
• bactericides/fungicides have so far been used in agriculture and horticulture to control diseases of rice plants, vegetables, fruit trees, flowering plants and other crop plants.
• Typical examples among them are benomyl (generic name: methyl 1-butylcarbamoyl-2-benzimidazolcarbamate), thiuram (generic name: bis(dimethylthiocarbamoyl) disulfide), oxolinic acid and the like.
• benomyl generic name: methyl 1-butylcarbamoyl-2-benzimidazolcarbamate
• thiuram generic name: bis(dimethylthiocarbamoyl) disulfide
• oxolinic acid oxolinic acid
• copper-based germicidal formulations which contain a copper compound, are characterized in that they are free of resistant strain development. Therefore, copper formulations containing cupric hydroxide, copper nonylphenolsulfonate or the like as an active ingredient are currently in general use.
• cupric hydroxide, copper nonylphenolsulfonate or the like as an active ingredient are currently in general use.
• it is essential to use them in high concentrations; such use in high concentrations result in manifestation of phytotoxicity and cause leaf burn and other injuries, hence is undesirable.
• Another object of the invention is to provide a germicidal composition for agricultural and horticultural use which will not cause chemical injuries such as leaf burn.
• a further object of the invention is to provide an environmentally safe germicidal composition for agricultural and horticultural use.
• a germicidal composition for agricultural and horticultural use which comprises an aldonic acid copper salt is provided.
• aldonic acid is a general term for the compound derived, from a chemical formula viewpoint, from an aldehyde group-containing monosaccharide (aldose) by oxidation of said aldehyde group.
• aldonic acid there may be mentioned compounds derived from such monosaccharides as aldotrioses (e.g. D-glyceraldehyde etc.), aldotetroses (e.g. D-erythrose etc.), aldopentoses (e.g.
• D-ribose, D-xylose, L-arabinose, etc. and aldohexoses (e.g. D-glucose, D-galactose, D-mannose, etc.) by oxidation of the aldehyde group thereof to a carboxyl group.
• aldohexoses e.g. D-glucose, D-galactose, D-mannose, etc.
• cupric (or copper(II)) gluconate is particularly preferred as the aldonic acid copper salt mentioned above.
• Said cupric salt is known as a food additive and very safe from an environmental viewpoint.
• either one single aldonic acid copper salt or a combination of two or more aldonic acid copper salts may be used.
• calcium carbonate may be added to the germicidal composition of the present invention.
• the germicidal composition of the invention may contain one or more of known insecticides, bactericides, fungicides, herbicides, fertilizers and like farm chemicals unless the effects of the invention are lessened.
• insecticides are, for instance, cyanophos, fenthion, fenitrothion, dichlofenthion, pirimiphos methyl, diazinon, isoxathion, pyridafenthion, chloropyrifos methyl, chloropyrifos, vamidothion, malathion, phenthoate, dimethoate, thiometon, phosalone, phosmet, methidathion, prothiophos, sulprofos, profenofos, pyraclofos, dichlorvos, monocrotophos, naled, chlorfenvinphos, acephate, EPN, ethion, carbaryl, fenobucarb, etiofencarb, pirimicarb, carbosulfan, benfracarb, methomyl, thiodicarb, alanicarb, biphenthrin,
• bactericdes and/or fungicides are inorganic copper, oxine-copper, inorganic sulfur, sodium hydrogen carbonate, potassium hydrogen carbonate, captan, dichlofluanide, chlorothalonil, fusaride, iprovenfos, edifenphos, phosethyl, thiophanate methyl, benomyl, thiabendazole, iprodione, vinclozolin, procymidone, fluorimide, metalaxyl, oxadixyl, triadimefon, bitertanol, myclobutanil, hexaconazole, propiconazole, difenoconazole, iproconazole, imibenconazole, triflumizole, proclanoz, peflazoate, fenarimol, pirifenox, trifolin, UBF-910, dithianon, quinomethionate, dino
• herbicides are, for example, fluazifop, quizalofop ethyl, aloxydim, cetoxydim and the like.
• the germicidal composition of the present invention may comprise the above-mentioned aldonic acid copper salt in powder form as such or may occur as an aqueous solution of the same.
• the water species to be used is not limited to any particular one but may be, for example, tap water, deionized water, activated carbon-treated water or distilled water.
• the concentration of the aldonic acid copper salt is not limited to any particlar level but may generally be 0 to less than 100% by weight, preferably about 5 to 90% by weight.
• the germicidal composition of the present invention may be prepared in the form of popular formulations such as spray formulations, wettable powders, emulsions, dusts, granules, etc. using appropriate carriers, surfactants and so on as necessary.
• Usable as the carriers are known ones such as clay, kaolin, bentonite, talc, acid clay, diatomaceous earth, calcium carbonate, nitrocellulose, starch, gum arabic, gaseous carbon dioxide, freons, benzene, kerosene, alcohols, acetone, xylene, methylnaphthalene, cyclohexane, animal fatty acid esters, potassium sulfate, potassium chloride, potassium nitrate, calcium dihydrogen phosphate, sodium sulfate, etc.
• surfactants are known ones such as lecithin, sucrose fatty acid esters, sorbitan fatty acid esters, monoglycerides, polypropylene glycol fatty acid esters, soaps, higher alcohol sulfate esters, alkylsulfonic acid salts, quaternary ammonium salts, polyalkylene oxides, sodium ligninsulfonate, sodium alkylbenzenesulfonates, sodium dinaphthylmethanesulfonate, sodium lauryl alcohol sulfate, polyoxyethylene alkylaryl ethers, etc.
• germicidal composition in applying the germicidal composition according to the present invention, known applicaiton methods can be widely employed. To be more concrete, such common methods as dipping, spraying, drenching arid the like can be employed. In applying to rice or such tuber plants as potato, paddy (unhulled rice) or seed potato is preferably subjected to dipping treatment. In the case of other crop plants, foliage application is preferred.
• the germicidal composition of the present invention Prior to application to crop plants, the germicidal composition of the present invention is diluted with water or some other diluent to an appropriate concentration.
• the concentration of the active ingredient aldonic acid copper salt may be suitably selected within a wide range according to the crop plant to be treated, the disease to be controlled, the stage of growth of the crop plant to be treated and the method of treatment, among others.
• a standard concentration is generally about 200 to 5,000 ppm (about 25 to 700 ppm as copper), preferably about 500 to 2,000 ppm (about 70 to 280 ppm as copper).
• a standard concentration is generally about 50 to 2,000 ppm (about 5 to 280 ppm as copper), preferably about 250 to 1,000 ppm (about 30 to 140 ppm as copper).
• the crop plant to be treated and the disease to be controlled with the germicidal composition of the present invention is not particularly limited but can include a wide variety.
• the target crop plant there may be mentioned, for example, rice, vegetables, fruit trees and flowering plants, and, as concrete examples of the target disease, there may be mentioned bacterial diseases as well as fungal diseases such as powdery mildew, late blight and downy mildew, among others.
• the germicidal composition of the present invention is particularly effective against the following crop plant diseases.
• the germicidal composition of the present invention is also effective in controlling pasthogenic microorganisms in nutrient solutions in nutriculture.
• the germicidal composition of the present invention is particularly effective against such pathogenic microorganisms as Erwinia species, Pseudomonas species, Xanthomonas species and like bacteria and mastigomycotina species and like fungi.
• the germicidal composition of the present invention shows an excellent germicidal effect not only upon ordinary bacteria and fungi but also upon strains resistant to chemicals.
• the germicidal composition of the present invention is effective in preventing disease damages to crop plants at markedly reduced concentrations as compared with the prior art copper preparations.
• the germicidal composition of the present invention upon application thereof, will not cause any chemical injury.
• the germicidal composition of the present invention is very low in environmental safety.
• a germicidal composition according to the present invention with an active ingredient concentration of 50% was prepared by admixing 50 parts by weight of cupric gluconate with 50 parts by weight of water.
• Example 1 rice bacterial seedling blight control test
• the germicidal composition of the invention as prepared in Formulation Example 1 was diluted with water to the active ingredient concentration indicated below in Table 1.
• the dilution was placed in a 100-ml beaker and 10 g of paddy infected with the causative microorganism of rice seedling blight was immersed therein for 24 hours.
• the thus-treated paddy was presoaked at 20°C for 3 days, then stimulated for germination at 32°C for 1 day, and sowed into a 12 x 12 cm plastic case.
• the sown case was maintained in a greenhouse at a temperature of 32°C for 2 days and then seedlings showing disease symptoms were counted 2 weeks after sowing.
• % Control (number of diseased seedlings in no treatment plot - number of diseased seedlings in treatment plot)/(number of diseased seedlings in no treatment plot) x 100
• % Control (number of diseased seedlings in no treatment plot - number of diseased seedlings in treatment plot)/(number of diseased seedlings in no treatment plot) x 100
• ppm Germicide Active ingredient concentration
• ppm Copper concentration
• Example 2 rice seeding rot by bacterial grain rot pathogen control test
• Example 2 The procedure of Example 1 was followed except that paddy infected with the causative microorganism of rice bacterial grain rot was used and diseased seedlings were counted 3 weeks after sowing. The control percentahe was calculated as decribed in Example 1. The results are shown in Table 2.
• Table 2 Germicide Copper concentration (ppm) % Control Phytotoxicity Germicide of invention 140 97 None Kocide Bordeaux 200 81 None Sterna - 97 None No treatment - 0 None
• the germicidal composition of the present invention as prepared in Formulation Example 1 was diluted with water to the active ingredient concentration indicated below in Table 3.
• a cucumber seedling at the single true leaf stage planted in a black vinyl pot was sprayed with 5 ml of the dilution and, 5 hours later, it was inoculated with the causative microorganism of cucumber bacterial spot by spraying.
• This cucumber seedling was kept under high-humidity conditions at 25°C for 7 days and then the area of lesion on the diseased leaves was determined and the lesion area percentage was calculated.
• the control percentage was calculated using the expression shown below.
• two germicides available on the market were also tested in the same manner. The results obtained are shown in Table 3.
• % Control (lesion area percentage in no treatment plot - lesion area percentage in treatment plot)/(lesion area percentage in no treatment plot) x 100
• Yonepon (tradename; active ingredient: copper nonylphenolsulfonate)
• the germicidal composition of the present invention as prepared in Formulation Example 1 was diluted with water to the active ingredient concentration indicated below in Table 4.
• a tomato seedling at the four true leaf stage planted in a black vinyl pot was sprayed with 5 ml of the dilution and, 5 hours later, inoculated with spores of the causative microorganism of tomato late blight by spraying.
• This tomato seedling was kept under high humidity conditions at 25°C for 7 days and then diseased leaves were counted.
• the control percentage was calculated as indicated in Example 3.
• a germicide available on the market was also tested in the same manner. The results obtained are shown in Table 4.
• Germicide Active ingredient concentration ppm
• Copper concentration ppm
• Control Phytotoxicity Germicide of invention 500 70 73 None 200 28 70 None 100 14 61 None Kocide Bordeaux 768 500 62 None 307 200 60 None 154 100 54 None No treatment - - 0 None Kocide Bordeaux (tradename; active ingredient: cupric hydroxide)
• the germicidal composition of the present invention as prepared in Formulation Example 1 was diluted with water to the active ingredient concentration indicated below in Table 5.
• a cucumber seedling at the single true leaf stage planted in a black vinyl pot was sprayed with 5 ml of the dilution and, 5 hours later, inoculated with spores of the benlate-resistant causa tive microorganism of cucumber powdery mildew by spraying.
• This cucumber seedling was kept in a greenhouse for 10 days and then diseased cucumber cotyledons were counted and the control percentage was calculated as indicated in Example 3.
• two germicides available on the market were also tested in the same manner. The results obtained are shown in Table 5.
• Germicide Active ingredient concentration ppm
• Copper concentration ppm
• Control Phytotoxicity Germicide of invention 500 70 61 None Kocide Bordeaux 768 500 30 Leaf burn Benlate 500 35 None No treatment - - 0 None Kocide Bordeaux (tradename; active ingredient: cupric hydroxide) Benlate (tradename; active ingredient: benomyl)
• Example 2 The procedure of Example 1 was followed except that paddy infected with the causative microorganism of rice "bakanae” disease was used and diseased seedlings were counted 4 weeks after sowing. The control percentage was calculated in the same manner. For comparison, two germicides available on the market were also tested in the same manner. The results are shown in Table 6. Table 6 Germicide Active ingredient concentration (ppm) Copper concentration (ppm) % Control Phytotoxicity Germicide of invention 2000 280 95 None 1000 140 84 None Kocide Bordeaux 214 143 47 None Benlate T 2000 - 31 None No treatment - - 0 None Kocide Bordeaux (tradename; active ingredient: cupric hydroxide) Benlate T (tradename; active ingredients: benomyl and thiuram)
• Example 7 Choinese cabbage bacterial soft rot control test
• the germicidal composition of the present invention as prepared in Formulation Example 1 was diluted with water to the respective active ingredient concentrations indicated below in Table 7.
• Japanese cabbage laminae injured with a bundle of needles were instantaneously dipped in one of the dilutions, air-dried and then inoculated with the causative microorganism of Chinese cabbage bacterial soft rot by placing on the needle lesion a paper disk impregnated with the causative microoganism. After maintaining in a plastic moist chamber for 4 days, diseased leaves were counted and the control percentage was calculated as indicated in Example 3. For comparison, a germicide available on the market was tested in the same manner. The results are shown in Table 7.
• Germicide Active ingredient concentration ppm
• Copper concentration ppm
• Control Phytotoxicity 500 70 100 None 200 28 100 None 100 14 63 None Kocide Bordeaux 768 500 100 Leaf burn 307 200 100 Leaf burn 154 100 63 None No treatment - - 0 None Kocide Bordeaux (tradename; active ingredient: cupric hydroxide)
• Example 1 The procedure of Example 1 was followed except that paddy infected with the causative microorganism of rice Helminthosporium leaf spot was used and diseased seedlings were counted 3 weeks after sowing. For comparison, a germicide available on the market was also tested in the same manner. The results are shown in Table 8.
• Table 8 Germicide Active ingredient concentration (ppm) Copper concentration (ppm) % Control Phytotoxicity Germicide of invention 1000 140 87 None Kocide Bordeaux 307 200 51 None No treatment - - 0 None Kocide Bordeaux (tradename; active ingredient: cupric hydroxide)
• the germicidal composition of the invention as prepared in Formulation Example 1 was diluted with water to the active ingredient concentration indicated below in Table 9 and the dilution was placed in a 100-ml beaker, and 10 g of paddy infected with the causative microorganism of rice damping-off was immersed therein for 24 hours. A portion of the thus-treated paddy was sowed onto a moistened filter paper placed in a petri dish and kept at 25°C for 3 days.
• Germicide Active ingredient concentration ppm
• Copper concentration ppm
• Control Phytotoxicity 1000 140 100 None Kocide Bordeaux 307 200 67 None No treatment - - 0 None Kocide Bordeaux (tradename; active ingredient: cupric hydroxide)

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• Life Sciences & Earth Sciences (AREA)
• Agronomy & Crop Science (AREA)
• Pest Control & Pesticides (AREA)
• Plant Pathology (AREA)
• Health & Medical Sciences (AREA)
• Engineering & Computer Science (AREA)
• Dentistry (AREA)
• General Health & Medical Sciences (AREA)
• Wood Science & Technology (AREA)
• Zoology (AREA)
• Environmental Sciences (AREA)
• Chemical & Material Sciences (AREA)
• Inorganic Chemistry (AREA)
• Agricultural Chemicals And Associated Chemicals (AREA)

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• 1994
  • 1994-05-17 JP JP6102747A patent/JPH07309703A/ja active Pending
• 1995
  • 1995-05-12 EP EP95918182A patent/EP0713645B1/fr not_active Expired - Lifetime
  • 1995-05-12 DE DE69527598T patent/DE69527598T2/de not_active Expired - Fee Related
  • 1995-05-12 KR KR1019960700202A patent/KR100381755B1/ko not_active IP Right Cessation
  • 1995-05-12 WO PCT/JP1995/000915 patent/WO1995031103A1/fr active IP Right Grant
  • 1995-05-16 TW TW084104859A patent/TW279781B/zh active

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